CN105153351B - Citric acid-polyacrylate magnetic hydrogel, preparation method and application thereof - Google Patents
Citric acid-polyacrylate magnetic hydrogel, preparation method and application thereof Download PDFInfo
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- CN105153351B CN105153351B CN201510464733.5A CN201510464733A CN105153351B CN 105153351 B CN105153351 B CN 105153351B CN 201510464733 A CN201510464733 A CN 201510464733A CN 105153351 B CN105153351 B CN 105153351B
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Abstract
The invention discloses a citric acid-polyacrylate magnetic hydrogel, a preparation method and an application thereof. A NaOH solution is added into acrylic acid with stirring; acrylamide is added; a cross-linking agent is added; after uniform mixing, magnetic Fe3O4 particles and citric acid are added; after dissolving, ammonium persulfate and sodium sulfite are added; after uniform mixing, heating and stirring are carried out at 70 DEG C till solidification; and after drying, the citric acid-polyacrylate magnetic hydrogel is obtained. The citric acid-polyacrylate magnetic hydrogel is a new environment-friendly adsorption material, which has large adsorption quantity without any influence to the soil pH value, and is convenient for recovery.
Description
Technical field
The present invention relates to a kind of citric acid-polyacrylate magnetic hydrogel, its preparation method and application.
Background technology
With the discharge and heavy metal pollution universality of " three wastes " in the commercial production such as chemical industry, plating, electronics and process hides, hidden
The characteristics of covering property, chronicity, irreversibility and Transport And Transformation, make heavy metal pollution to the harm of ecosystem and strong to human body
The impact of health is of increasing concern, for the improvement of heavy metal pollution seems very urgent.At present, heavy-metal contaminated soil is repaiied
Multiple mainly to adopt physical-chemical process, its mechanism is the existing forms for changing heavy metal in soil so as to be changed into by activated state
Stable state is so as to reducing its animal migration and bioavailability in the environment；Or removing heavy metals are removed from soil, so that it is deposited
Concentration is stayed close to or up background value.Hydrogel the advantages of the water suction of its uniqueness and good biocompatibility because repairing weight
Paid close attention in metallic pollution.But application of the citric acid-polyacrylate magnetic hydrogel on absorption copper ion does not temporarily appear in the newspapers
Road.
The content of the invention
It is an object of the invention to overcome the deficiencies in the prior art part, there is provided a kind of citric acid-polyacrylate magnetic
Property hydrogel, its preparation method and application, it is big with adsorbance, do not affect soil pH value, be easy to the advantages of reclaiming, be a kind of new
Environmentally friendly adsorbing material.
One of the technical solution adopted for the present invention to solve the technical problems is：
A kind of preparation method of citric acid-polyacrylate magnetic hydrogel, takes acrylic acid, drips in acrylic acid under stirring
The NaOH solution for plus 30%, adds acrylamide, and mix homogeneously adds cross-linking agent, after mix homogeneously, adds magnetic Fe3O4Grain
Son simultaneously makes it fully dissolve, and adds citric acid, after 0.05mol/L ammonium persulfate solutions are added after dissolving, adds in 20~30s
0.05mol/L sodium sulfite solutions, mix homogeneously, to solidifying, 55~65 DEG C of drying are obtained final product described heated and stirred at 65~75 DEG C
Citric acid-polyacrylate magnetic hydrogel；The acrylic acid, 30% NaOH solution, acrylamide, cross-linking agent, magnetic
Fe3O4Particle, citric acid, 0.05mol/L ammonium persulfate solutions, 0.05mol/L sodium sulfite solutions formula proportion be 4.5~
5.5g：6~7ml：1.2~1.3g:0.0018~0.0022g:0.08~0.12g:0.8~5.5g:2.0ml~2.4ml:3.7
~4.1ml.
In one embodiment：The heated and stirred to the temperature for solidifying is 70 DEG C；The drying temperature is 60 DEG C；The propylene
Acid, 30% NaOH solution, acrylamide, cross-linking agent, magnetic Fe3O4Particle, citric acid, 0.05mol/L ammonium persulfate solutions,
The formula proportion of 0.05mol/L sodium sulfite solutions is 5g：6.5ml:1.25g:0.002g:0.1g:1~5g:2.2ml:
3.9ml。
In one embodiment：The acrylic acid, 30% NaOH solution, acrylamide, cross-linking agent, magnetic Fe3O4Particle, lemon
Lemon acid, the formula proportion of 0.05mol/L ammonium persulfate solutions, 0.05mol/L sodium sulfite solutions are 5g：6.5ml:1.25g:
0.002g:0.1g:2.5g:2.2ml:3.9ml。
In one embodiment：The magnetic Fe3O4The preparation method of particle is：Take FeCl3·6H2O and FeCl2·4H2O, nitrogen
It is soluble in water under gas shielded, 25~35min is stirred, 55~65 DEG C are heated under nitrogen protection, it is 8.8~9.2 to adjust pH value,
Fe is produced under the alkalescence condition3O4Crystal, after being cooled to room temperature, Magnet precipitation separation, as magnetic Fe3O4Particle；It is described
FeCl3·6H2O and FeCl2·4H2The mol ratio of O is 0.04~0.05:0.03~0.04.
In one embodiment：The cross-linking agent is N,N methylene bis acrylamide.
The two of the technical solution adopted for the present invention to solve the technical problems are：
A kind of citric acid-polyacrylate magnetic hydrogel, the raw material of the magnetic hydrogel include acrylic acid, 30%
NaOH solution, acrylamide, cross-linking agent, magnetic Fe3O4Particle, citric acid, 0.05mol/L ammonium persulfate solutions, 0.05mol/L
Sodium sulfite solution；And the acrylic acid, 30% NaOH solution, acrylamide, cross-linking agent, magnetic Fe3O4Particle, lemon
Lemon acid, the formula proportion of 0.05mol/L ammonium persulfate solutions, 0.05mol/L sodium sulfite solutions are 4.5~5.5g：6~7ml：
1.2~1.3g:0.0018~0.0022g:0.08~0.12g:0.8~5.5g:2.0ml~2.4ml:3.7~4.1ml.
The three of the technical solution adopted for the present invention to solve the technical problems are：
Application of the above-mentioned citric acid-polyacrylate magnetic hydrogel on absorption copper ion.
In one embodiment：Absorption copper ion condition be：52~58 DEG C of temperature, pH value is 2.8~3.2, absorption 22~
26h, Cu2+Initial concentration is not higher than 25mg/L.
Compared with background technology, it has the advantage that the technical program：
Because citric acid contains three carboxyls, heavy metal has stronger complexing, because it is easy to dissolving, so right
It is widely used in the absorption behavior of heavy metal-polluted soil.But citric acid is acidity, and soil pH can be changed after being manured into soil, affect
The activity of microorganism.Citric acid-polyacrylate the magnetic hydrogel of the present invention, is repaiied using two kinds of citric acid and polyacrylate
Multiple agent is compound to be prepared, and adds magnetic Fe3O4Particle, not only facilitates the recovery of hydrogel, also add the suction of hydrogel
Attached capacity, while citric acid is heavy metal ion adsorbed to copper ion etc., reduces acidization of the citric acid to soil, no
Affect soil pH value and the wherein activity of microorganism, a kind of new environmentally friendly adsorbing material.
Description of the drawings
With reference to the accompanying drawings and examples the invention will be further described.
Fig. 1 is variable concentrations Cu2+Ultra-violet absorption spectrum.
Fig. 2 is absorbance A and Cu2+The standard curve schematic diagram of concentration C.
Fig. 3 is the citric acid-polyacrylate magnetic hydrogel and the non magnetic water-setting of citric acid-polyacrylate of the present invention
Absorption property contrast schematic diagram of the glue to copper ion.
Fig. 4 is the citric acid-polyacrylate magnetic hydrogel water absorption rate schematic diagram of embodiment 1~5.
Fig. 5 is the copper absorption rate schematic diagram of the citric acid-polyacrylate magnetic hydrogel of embodiment 1~5.
Fig. 6 is the infared spectrum of the citric acid-polyacrylate magnetic hydrogel of the present invention.
Specific embodiment
Present disclosure is illustrated below by embodiment：
Embodiment 1~5
A kind of citric acid-polyacrylate magnetic hydrogel, its preparation method is as follows：
According to proportioning raw materials in table 1, acrylic acid (AA) is weighed in 100ml beakers, to Deca in acrylic acid under stirring
30% NaOH solution, after the two reaction, adds acrylamide (AM), after mix homogeneously, adds cross-linking agent N, N- methylenes
Base bisacrylamide (MBA), after sonic oscillation is with mix homogeneously, adds magnetic Fe3O4Particle, sonic oscillation makes it fully dissolve,
Citric acid is added, is added after 0.05mol/L ammonium persulfate solutions after sonic oscillation dissolving, 0.05mol/L is added in 20~30s
Sodium sulfite solution, mix homogeneously is put into heated and stirred in 70 DEG C of water-baths and, to solidifying, places in 60 DEG C of baking ovens and dry, i.e.,
Obtain described citric acid-polyacrylate magnetic hydrogel.
The formula of citric acid-polyacrylate magnetic hydrogel in the embodiment 1~5 of table 1
Wherein, magnetic Fe3O4Particle is prepared using part coprecipitation：12.2g is sequentially added in 250mL three-neck flasks
FeCl3·6H2O and 7g FeCl2·4H2O, is dissolved in 100ml distilled water, high-speed stirred 30min under nitrogen protection, nitrogen protection
To 60 DEG C, it is 9 that Deca ammonia adjusts pH value to lower heating in water bath, and under the alkalescence condition of ammonia Fe is produced3O4Black crystals, cooling
To room temperature, Magnet precipitation separation, deionized water and dehydrated alcohol are cleaned repeatedly, as magnetic Fe3O4Particle.Reaction equation is such as
Under：
Fe2++2Fe3++8OH-=Fe3O4↓+4H2O
Embodiment 6：Citric acid-polyacrylate magnetic hydrogel is inhaled with the non magnetic hydrogel of citric acid-polyacrylate
Attached performance comparison
The BCO for taking 0.2g is dissolved in 100mL dehydrated alcohol, plus the H of 100mL2O is obtained the BCO that mass concentration is 0.1%
Solution；5.4g chloride leaches are taken in water, plus 35mL ammonia, 100mL is diluted to, ammonium chloride-ammonia buffer is obtained, adjust
PH value to 8.5 is standby.
In the color comparison tube of 25mL, 0mL (reference), the 10.0mg/L of 2mL, 4mL, 6mL, 8mL, 10mL are separately added into
Cu2+Titer, then the BCO developers of the 1g/L of the pH=8.5 ammonium chloride-ammonia buffer and 5mL of 5mL are separately added into, plus go
Ionized water is settled to scale, shakes up.After fully colour developing 1h, Cu is measured using ultraviolet spectrophotometer2+Ultra-violet absorption spectrum such as
Fig. 1, absorbance and Cu2+The linear relationship of concentration C such as Fig. 2, the Cu in certain scope2+Concentration has good with absorbance
Linear relationship, absorbance A and Cu2+The relational expression of solution concentration C：A=0.0107+0.29338*C, its coefficient R=
0.99977.This standard curve is used for into the Cu of embodiment 6~162+Concentration Testing.
The same citric acid of the preparation method-polyacrylate magnetic hydrogel of the non magnetic hydrogel of citric acid-polyacrylate
Preparation method, but be not added with magnetic Fe3O4Particle.
Citric acid-polyacrylate the magnetic hydrogel and citric acid-polyacrylate non-magnetic of 0.2g are accurately weighed respectively
Property hydrogel, be placed in excessive deionized water immersion absorption, after hydrogel reaches equilibrium swelling, taking-up filter paper blots table
The moisture in face, is put in the conical flask of 150mL respectively, then is separately added into the 10mg/L Cu of 50mL2+Solution, conical flask is put into
In water-bath constant temperature oscillator, 120r/min, after vibration absorption 24h, is filtered by 25 DEG C, takes 2mL filtrates, add the ammonium chloride of 5mL-
Ammonia buffer and 5mL BCO solution, mix homogeneously after standing 1h, is detected and root with UV-2550 ultraviolet-uisible spectrophotometers
Its Cu is obtained according to above-mentioned standard curve2+Concentration, and then obtain Cu2+Adsorption rate.
Experimental result is as shown in figure 3, vibrate after 24h, the non magnetic hydrogel adsorption rate of citric acid-polyacrylate
84.49%, less than citric acid-polyacrylate magnetic hydrogel adsorption rate 88.12%, difference 1.67%.Illustrate magnetic water-setting
The absorption property of glue is better than non magnetic hydrogel.
Embodiment 7：The water absorption rate of the citric acid of embodiment 1~5-polyacrylate magnetic hydrogel
Citric acid-polyacrylate the magnetic hydrogel of 0.2g embodiments 1~5 is accurately weighed respectively, and under room temperature foot is placed in
Soak in amount deionized water, take out every 1h, drain the moisture on surface, weigh and record data.After record, be put into again from
Soak in sub- water, until adsorption saturation.
Experimental result is as shown in figure 4, after absorption 9h, weight is basically unchanged, and illustrates citric acid-polyacrylate magnetic water-setting
Glue adsorption saturation.The citric acid of embodiment 1~5-polyacrylate magnetic hydrogel water absorption rate is respectively：111.11、
114.79th, 132.16,22.16,16.37, the citric acid-polyacrylate magnetic hydrogel water absorption rate highest of embodiment 3 is implemented
The citric acid of example 5-polyacrylate magnetic hydrogel water absorption rate is minimum.
Embodiment 8：The copper absorption rate of the citric acid of embodiment 1~5-polyacrylate magnetic hydrogel
Citric acid/polyacrylate the magnetic hydrogel of 0.2g embodiments 1~5 is accurately weighed respectively, is placed in certain volume
Deionized water in immersion absorption, after hydrogel reaches equilibrium swelling, taking-up filter paper blots the moisture on surface, is put in respectively
In the conical flask of 5 150mL, then the 10mg/LCu for being separately added into 50mL2+Solution, by conical flask water-bath constant temperature oscillator is put into
In, 120r/min, after vibration absorption 24h, is filtered by 25 DEG C, takes 2mL filtrates, adds the ammonium chloride-ammonia buffer and 5mL of 5mL
BCO solution, mix homogeneously, after standing 1h, with the detection of UV-2550 ultraviolet-uisible spectrophotometers and according to the standard of embodiment 6
Curve obtains its Cu2+Concentration, and then obtain Cu2+Adsorption rate.
Experimental result is as shown in figure 5, the citric acid-polyacrylate magnetic hydrogel of embodiment 1~5 is to Cu2+Absorption
Rate is respectively：88.52%th, 89.73%, 90.78%, 83.43%, 80.75%.The citric acid of embodiment 3-polyacrylate magnetic
Property hydrogel adsorption rate for best.
Embodiment 9
Citric acid/polyacrylate the magnetic hydrogel of 0.2g embodiments 3 is accurately weighed respectively, is placed in going for certain volume
Immersion absorption in ionized water, after hydrogel reaches equilibrium swelling, taking-up filter paper blots the moisture on surface, is put in 150mL's
In conical flask, the 20mg/LCu of 50mL is added2+Solution, with the NaOH solution and the HCl solution difference of 0.3mol/ of 0.1mol/L
The pH for adjusting solution is 3, conical flask is put in water-bath constant temperature oscillator, 120r/min, 55 DEG C, after vibration absorption 24h, mistake
Filter, takes 2mL filtrates, adds the ammonium chloride-ammonia buffer and 5mL BCO solution of 5mL, mix homogeneously after standing 1h, to use UV-
2550 ultraviolet-uisible spectrophotometers are detected and obtain its Cu according to the standard curve of embodiment 62+Concentration, and then obtain Cu2+Inhale
Attached rate.
After testing, Cu2+Adsorption rate is 93.27%.
Embodiment 10
Citric acid/polyacrylate the magnetic hydrogel of 0.2g embodiments 3 is accurately weighed respectively, is placed in going for certain volume
Immersion absorption in ionized water, after hydrogel reaches equilibrium swelling, taking-up filter paper blots the moisture on surface, is put in 150mL's
In conical flask, the 10mg/LCu of 50mL is added2+Solution, with the NaOH solution and the HCl solution difference of 0.3mol/ of 0.1mol/L
The pH for adjusting solution is 3, conical flask is put in water-bath constant temperature oscillator, 120r/min, 25 DEG C, after vibration absorption 24h, mistake
Filter, takes 2mL filtrates, adds the ammonium chloride-ammonia buffer and 5mL BCO solution of 5mL, mix homogeneously after standing 1h, to use UV-
2550 ultraviolet-uisible spectrophotometers are detected and obtain its Cu according to the standard curve of embodiment 62+Concentration, and then obtain Cu2+Inhale
Attached rate.
After testing, Cu2+Adsorption rate is 91.70%.
Embodiment 11
Citric acid/polyacrylate the magnetic hydrogel of 0.2g embodiments 3 is accurately weighed respectively, is placed in going for certain volume
Immersion absorption in ionized water, after hydrogel reaches equilibrium swelling, taking-up filter paper blots the moisture on surface, is put in 150mL's
In conical flask, the 10mg/LCu of 50mL is added2+Solution, with the NaOH solution and the HCl solution difference of 0.3mol/ of 0.1mol/L
The pH for adjusting solution is 6, conical flask is put in water-bath constant temperature oscillator, 120r/min, 25 DEG C, after vibration absorption 24h, mistake
Filter, takes 2mL filtrates, adds the ammonium chloride-ammonia buffer and 5mL BCO solution of 5mL, mix homogeneously after standing 1h, to use UV-
2550 ultraviolet-uisible spectrophotometers are detected and obtain its Cu according to the standard curve of embodiment 62+Concentration, and then obtain Cu2+Inhale
Attached rate.
After testing, Cu2+Adsorption rate is 89.16%.
Embodiment 12
Citric acid/polyacrylate the magnetic hydrogel of 0.2g embodiments 3 is accurately weighed respectively, is placed in going for certain volume
Immersion absorption in ionized water, after hydrogel reaches equilibrium swelling, taking-up filter paper blots the moisture on surface, is put in 150mL's
In conical flask, the 20mg/LCu of 50mL is added2+Solution, with the NaOH solution and the HCl solution difference of 0.3mol/ of 0.1mol/L
The pH for adjusting solution is 1, and conical flask is put in water-bath constant temperature oscillator, is adsorbed at 35 DEG C after 24h, is filtered, and takes 2mL filtrates,
Add the ammonium chloride-ammonia buffer and 5mL BCO solution of 5mL, mix homogeneously, after standing 1h, with UV-2550 UV, visible light point
Light photometer is detected and obtains its Cu according to the standard curve of embodiment 62+Concentration, and then obtain Cu2+Adsorption rate.
After testing, Cu2+Adsorption rate is 91.43%.
Embodiment 13
Citric acid/polyacrylate the magnetic hydrogel of 0.2g embodiments 3 is accurately weighed respectively, is placed in going for certain volume
Immersion absorption in ionized water, after hydrogel reaches equilibrium swelling, taking-up filter paper blots the moisture on surface, is put in 150mL's
In conical flask, the 160mg/LCu of 50mL is added2+Solution, with the NaOH solution and the HCl solution point of 0.3mol/ of 0.1mol/L
Not Tiao Jie solution pH be 5, conical flask is put in water-bath constant temperature oscillator, at 45 DEG C adsorb 24h after, filter, take 2mL filter
Liquid, add 5mL ammonium chloride-ammonia buffer and 5mL BCO solution, mix homogeneously, stand 1h after, with UV-2550 is ultraviolet can
See that spectrophotometer is detected and obtains its Cu according to the standard curve of embodiment 62+Concentration, and then obtain Cu2+Adsorption rate.
After testing, Cu2+Adsorption rate is 85.21%.
Embodiment 14
Citric acid/polyacrylate the magnetic hydrogel of 0.2g embodiments 3 is accurately weighed respectively, is placed in going for certain volume
Immersion absorption in ionized water, after hydrogel reaches equilibrium swelling, taking-up filter paper blots the moisture on surface, is put in 150mL's
In conical flask, the 10mg/LCu of 50mL is added2+Solution, with the NaOH solution and the HCl solution difference of 0.3mol/ of 0.1mol/L
The pH for adjusting solution is 2, and conical flask is put in water-bath constant temperature oscillator, is adsorbed at 65 DEG C after 24h, is filtered, and takes 2mL filtrates,
Add the ammonium chloride-ammonia buffer and 5mL BCO solution of 5mL, mix homogeneously, after standing 1h, with UV-2550 UV, visible light point
Light photometer is detected and obtains its Cu according to the standard curve of embodiment 62+Concentration, and then obtain Cu2+Adsorption rate.
After testing, Cu2+Adsorption rate is 87.79%.
Embodiment 15
Citric acid/polyacrylate the magnetic hydrogel of 0.2g embodiments 3 is accurately weighed respectively, is placed in going for certain volume
Immersion absorption in ionized water, after hydrogel reaches equilibrium swelling, taking-up filter paper blots the moisture on surface, is put in 150mL's
In conical flask, the 80mg/LCu of 50mL is added2+Solution, with the NaOH solution and the HCl solution difference of 0.3mol/ of 0.1mol/L
The pH for adjusting solution is 3, and conical flask is put in water-bath constant temperature oscillator, is adsorbed at 25 DEG C after 24h, is filtered, and takes 2mL filtrates,
Add the ammonium chloride-ammonia buffer and 5mL BCO solution of 5mL, mix homogeneously, after standing 1h, with UV-2550 UV, visible light point
Light photometer is detected and obtains its Cu according to the standard curve of embodiment 62+Concentration, and then obtain Cu2+Adsorption rate.
After testing, Cu2+Adsorption rate is 89.63%.
Embodiment 16
Citric acid/polyacrylate the magnetic hydrogel of 0.2g embodiments 3 is accurately weighed respectively, is placed in going for certain volume
Immersion absorption in ionized water, after hydrogel reaches equilibrium swelling, taking-up filter paper blots the moisture on surface, is put in 150mL's
In conical flask, the 40mg/LCu of 50mL is added2+Solution, with the NaOH solution and the HCl solution difference of 0.3mol/ of 0.1mol/L
The pH for adjusting solution is 4, conical flask is put in water-bath constant temperature oscillator, 120r/min, 55 DEG C, after vibration absorption 24h, mistake
Filter, takes 2mL filtrates, adds the ammonium chloride-ammonia buffer and 5mL BCO solution of 5mL, mix homogeneously after standing 1h, to use UV-
2550 ultraviolet-uisible spectrophotometers are detected and obtain its Cu according to the standard curve of embodiment 62+Concentration, and then obtain Cu2+Inhale
Attached rate.
After testing, Cu2+Adsorption rate is 91.24%.
Above-described embodiment is capable of achieving the effect of following experimental examples：
Experimental example 1：The infrared analysiss of citric acid-polyacrylate magnetic hydrogel
The infrared analysiss of citric acid-polyacrylate magnetic hydrogel are as shown in fig. 6,1401,990cm-1Place's absworption peak point
Hydroxyl in-plane bending vibration peak that Wei be on citric acid carboxyl and out-of-plane bending vibration peak；567cm-1The new peak that place occurs, be
Fe304The bending vibration of middle Fe-O, shows that hydrogel successfully loads Fe3O4；1750cm-1Locate to be inhaled for the feature of carboxylic carbonyl C=O
Receive peak；1520cm-1For the characteristic peak of carboxylate.The infrared analysiss result is represented and successfully define citric acid-polyacrylate magnetic
Property hydrogel.
In sum, the optimum material proportion of citric acid-polyacrylate magnetic hydrogel is：Acrylic acid and citric acid
Mass ratio is 2:1, the formula proportion of acrylic acid and 30% NaOH solution is 5g：6.5ml, i.e. degree of neutralization are 70~80%, third
Acrylamide quality for acrylic acid quality 25%, cross-linking agent MBA for acrylic acid quality 0.04%, 0.05mol/L Ammonium persulfate .s,
0.05mol/L sodium sulfite is 0.05%, the 0.1g Fe of acrylic acid quality3O4, adsorption effect is optimal when solidification temperature is 70 DEG C；
And optimal adsorption Cu2+Condition be：55 DEG C of temperature, pH value is 3,120r/min vibration absorption 24h, Cu2+Initial concentration is not higher than
20mg/L。
Those of ordinary skill in the art understand, when the technical parameter of the present invention changes in following scope, it is contemplated that
Obtain technique effect same as the previously described embodiments or close：
A kind of preparation method of citric acid-polyacrylate magnetic hydrogel, takes acrylic acid, drips in acrylic acid under stirring
The NaOH solution for plus 30%, adds acrylamide, and mix homogeneously adds cross-linking agent, after mix homogeneously, adds magnetic Fe3O4Grain
Son simultaneously makes it fully dissolve, and adds citric acid, after 0.05mol/L ammonium persulfate solutions are added after dissolving, adds in 20~30s
0.05mol/L sodium sulfite solutions, mix homogeneously, to solidifying, 55~65 DEG C of drying are obtained final product described heated and stirred at 65~75 DEG C
Citric acid-polyacrylate magnetic hydrogel；The acrylic acid, 30% NaOH solution, acrylamide, cross-linking agent, magnetic
Fe3O4Particle, citric acid, 0.05mol/L ammonium persulfate solutions, 0.05mol/L sodium sulfite solutions formula proportion be 4.5~
5.5g：6~7ml：1.2~1.3g:0.0018~0.0022g:0.08~0.12g:0.8~5.5g:2.0ml~2.4ml:3.7
~4.1ml.
The heated and stirred to the temperature for solidifying is 70 DEG C；The drying temperature is 60 DEG C；The acrylic acid, 30%
NaOH solution, acrylamide, cross-linking agent, magnetic Fe3O4Particle, citric acid, 0.05mol/L ammonium persulfate solutions, 0.05mol/L
The formula proportion of sodium sulfite solution is 5g：6.5ml:1.25g:0.002g:0.1g:1~5g:2.2ml:3.9ml.
The acrylic acid, 30% NaOH solution, acrylamide, cross-linking agent, magnetic Fe3O4Particle, citric acid,
0.05mol/L ammonium persulfate solutions, the formula proportion of 0.05mol/L sodium sulfite solutions are 5g：6.5ml:1.25g:0.002g:
0.1g:2.5g:2.2ml:3.9ml。
The magnetic Fe3O4The preparation method of particle is：Take FeCl3·6H2O and FeCl2·4H2O, is dissolved under nitrogen protection
In water, 25~35min is stirred, under nitrogen protection 55~65 DEG C are heated to, it is 8.8~9.2 to adjust pH value, under the alkalescence condition
Produce Fe3O4Crystal, after being cooled to room temperature, Magnet precipitation separation, as magnetic Fe3O4Particle；The FeCl3·6H2O and
FeCl2·4H2The mol ratio of O is 0.04~0.05:0.03~0.04.
The cross-linking agent is N,N methylene bis acrylamide.
A kind of citric acid-polyacrylate magnetic hydrogel, the raw material of the magnetic hydrogel include acrylic acid, 30%
NaOH solution, acrylamide, cross-linking agent, magnetic Fe3O4Particle, citric acid, 0.05mol/L ammonium persulfate solutions, 0.05mol/L
Sodium sulfite solution；And the acrylic acid, 30% NaOH solution, acrylamide, cross-linking agent, magnetic Fe3O4Particle, lemon
Lemon acid, the formula proportion of 0.05mol/L ammonium persulfate solutions, 0.05mol/L sodium sulfite solutions are 4.5~5.5g：6~7ml：
1.2~1.3g:0.0018~0.0022g:0.08~0.12g:0.8~5.5g:2.0ml~2.4ml:3.7~4.1ml.
Application of the above-mentioned citric acid-polyacrylate magnetic hydrogel on absorption copper ion.
Wherein, the condition of absorption copper ion is：52~58 DEG C of temperature, pH value is 2.8~3.2, adsorbs 22~26h, Cu2+Just
Beginning concentration is not higher than 25mg/L.
The above, only present pre-ferred embodiments, therefore can not according to this limit the scope of present invention enforcement, i.e., according to
Equivalence changes that the scope of the claims of the present invention and description are made and modification, all should still belong in the range of the present invention covers.
Claims (8)
1. the preparation method of a kind of citric acid-polyacrylate magnetic hydrogel, it is characterised in that：Take acrylic acid, under stirring to
The NaOH solution of Deca 30% in acrylic acid, adds acrylamide, and mix homogeneously adds cross-linking agent, after mix homogeneously, adds
Magnetic Fe3O4Particle simultaneously makes it fully dissolve, and adds citric acid, adds 0.05mol/L ammonium persulfate solutions after dissolving, 20~
0.05mol/L sodium sulfite solutions, mix homogeneously, heated and stirred extremely solidification at 65~75 DEG C, 55~65 DEG C of bakings are added in 30s
It is dry, obtain final product described citric acid-polyacrylate magnetic hydrogel；The acrylic acid, 30% NaOH solution, acrylamide,
Cross-linking agent, magnetic Fe3O4Particle, citric acid, 0.05mol/L ammonium persulfate solutions, the formula of 0.05mol/L sodium sulfite solutions
Ratio is 4.5~5.5g：6~7ml：1.2~1.3g:0.0018~0.0022g:0.08~0.12g:0.8~5.5g:2.0ml
~2.4ml:3.7~4.1ml.
2. a kind of preparation method of citric acid-polyacrylate magnetic hydrogel according to claim 1, its feature exists
In：The heated and stirred to the temperature for solidifying is 70 DEG C；The drying temperature is 60 DEG C；The acrylic acid, 30% NaOH are molten
Liquid, acrylamide, cross-linking agent, magnetic Fe3O4Particle, citric acid, 0.05mol/L ammonium persulfate solutions, 0.05mol/L sulfurous acids
The formula proportion of sodium solution is 5g：6.5ml:1.25g:0.002g:0.1g:1~5g:2.2ml:3.9ml.
3. a kind of preparation method of citric acid-polyacrylate magnetic hydrogel according to claim 1, its feature exists
In：The acrylic acid, 30% NaOH solution, acrylamide, cross-linking agent, magnetic Fe3O4Particle, citric acid, 0.05mol/L mistakes
Ammonium sulfate, the formula proportion of 0.05mol/L sodium sulfite solutions are 5g：6.5ml:1.25g:0.002g:0.1g:2.5g:
2.2ml:3.9ml。
4. a kind of preparation method of citric acid-polyacrylate magnetic hydrogel according to claim 1, its feature exists
In：The magnetic Fe3O4The preparation method of particle is：Take FeCl3·6H2O and FeCl2·4H2O, it is soluble in water under nitrogen protection,
25~35min of stirring, under nitrogen protection 55~65 DEG C are heated to, and it is 8.8~9.2 to adjust pH value, is produced under the alkalescence condition
Fe3O4Crystal, after being cooled to room temperature, Magnet precipitation separation, as magnetic Fe3O4Particle；The FeCl3·6H2O and FeCl2·
4H2The mol ratio of O is 0.04~0.05:0.03~0.04.
5. a kind of preparation method of citric acid-polyacrylate magnetic hydrogel according to claim 1, its feature exists
In：The cross-linking agent is N,N methylene bis acrylamide.
6. the citric acid prepared by a kind of preparation method according to claim 1 or 4 or 5-polyacrylate magnetic water-setting
Glue, it is characterised in that：The raw material of the magnetic hydrogel include acrylic acid, 30% NaOH solution, acrylamide, cross-linking agent,
Magnetic Fe3O4Particle, citric acid, 0.05mol/L ammonium persulfate solutions, 0.05mol/L sodium sulfite solutions；And the acrylic acid,
30% NaOH solution, acrylamide, cross-linking agent, magnetic Fe3O4Particle, citric acid, 0.05mol/L ammonium persulfate solutions,
The formula proportion of 0.05mol/L sodium sulfite solutions is 4.5~5.5g：6~7ml：1.2~1.3g:0.0018~0.0022g:
0.08~0.12g:0.8~5.5g:2.0ml~2.4ml:3.7~4.1ml.
7. application of the citric acid according to claim 6-polyacrylate magnetic hydrogel on absorption copper ion.
8. application according to claim 7, it is characterised in that：Absorption copper ion condition be：52~58 DEG C of temperature, pH value
For 2.8~3.2, adsorb 22~26h, Cu2+Initial concentration is not higher than 25mg/L.
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